Diallylamino phenyl n-methyl carbamates



United States Patent The present invention relates to and has as its object processes for the production of new and useful insecticidal diallylaminophenyl-N-methyl carbamic acid esters of the general formula 3,2l0A03 Patented Oct. 5, 1965 or bis(-diallylaminophenyl)-carbonic acid ester from the aforesaid aminophenols and phosgene of the general formula ice and to react these with methylor dimethyl amine. Finally the products of the process are accessible by transesterification of the above shown diallylaminophenols with N-methylor N,N-dimethyl-phenyl carbamate.

With respect to the insecticidal effect, the carbamic acid 9 CH3 esters obtainable according to the rocess are clearly su e- P P 2 -OC-N nor to the 3-d1methylammophenyl-N-methyl carbamate :t: g having analogous structure and employed for the same I 2 purpose, as is apparent from the experimental results 0 which follow.

Biological activity Compound Active agent, Percent Applied against percent deaths concentra of pests tion Caterpillars (Plutella 0. 2 100 O CNH CH3 Maculipennis). 0.02 0 H Dew flies (Drosophila 0.2 0 N O Mzlan ogaster). Aphids (Aphis fabae). 8:3 28 CH3 CH9 Spider mites (Tetrany- 0.2

thus telarius).

- 0.2 100 Caterpillars (Plutella O CECE: Maculipenm's). 33 38 I O Dew flies (Drosophila O. 2 8O Melanugaster). N(CHZOHCH2) Aphids (Apllt s fabae) 8- 3 CH Caterpillars (Plutella 0.2 100 I Maculz'penm's). 0, 02 100 Dew [lies (Drosophila 0. 2 70 (CH CHCH2)2N O-C-NH CH Melanogaster).

1] Spider mites (Tetrtmy- 0.2 100 $11 0 chus telarius). 0.02 40 in which R stands for hydrogen or a methyl group, R is a lower alkyl radical or a halogen atom and n is equal to 0, l or 2 as well as the new compounds shown before.

It has been found that carbamic acid esters of the above mentioned formula, including those compounds wherein the substituted amino group on the phenyl ring is ortho amino or para amino, possess distinctive insecticidal properties and are therefore outstandingly suitable for combating plant pest insects, especially aphids, spider mites and caterpillars.

The production of compounds according to the invention proceeds according to known processes by reaction of the corresponding diallylaminophenol (Ros N(OH CH=CI-I with methylisocyanate or methylor dimethyl-carbamic acid chloride. It is further possible to produce first the diallylarninophenyl ester of chloroforrnic acid of the general formula The use of the products of the process as pest control agents or plant protection agents proceeds in the usual way, i.e. preferably in admixture with solid or liquid extending or diluting agents, e.g. talc, chalk, soot, kieselguhr, bentoni'te, vermiculite and the like. For the production of liquid formulations water is primarily used as diluent, the simultaneous application of solvent assistants such as acetone, dimethyl forrnamide, o-chlorobenzene, xylene, and emulsifiers, being for the most part necessary or expedient, since the carbarnic acid esters according to the invention are to a large extent water-insoluble. As emulsifiers those of a non-ionic type have proved to be especially suitable, e.g. polyglycol ethers of phenols. The following examples illustrate the process claimed.

Example 1 N(cH,-oH=oH, 2 18.9 g. (0.1 mol) of Z-diallylphenol are dissolved in anhydrous benzene and this solution is treated first with 6.3 g. (0.11 mol) of methyl isocyanate and then with 3 drops of triethylamine. A vigorous reaction occurs with heating of the mixture. After standing for one day, the benzene solution is washed with water, dried over sodium sulphate, and the solvent is then distilled off under vacuum. As residue there are obtained 19.8 g. of 2-dia1lylaminophenyl-N-methyl carbamate of MP. 39 to 40 C.

The 2-diallylaminophenol used as starting material is produced according to known methods by reaction of 2- aminophenol with allyl chloride in aqueous sodium bicarbonate solution.

By the same Way there may be obtained the compounds of the following formulae:

Example 2 Under reaction conditions analogous to those of Example 1, 20.4 g. of 3,5-dimethyl-4-diallylaminophenyTN- methyl carbarnate of melting point 61 to 62 C. are obtained from 21.7 g. (0.1 mol) of 3,S-dimethyl-4-diallylaminophenol and 6.3 g. (0.11 mol) of methyl isocyanate.

Example 3 CH3 CH3 Under condition reactions analogous to those of Example 1, 24.2 g. of 3-isopropy1-4-diallylamino-phenyl-N- methyl carbamate are obtained by reaction of 23.1 g. (0.1 mol) 3-isopropyl-4-diallylamino-phenol and 6.3 g. methylisocyanate.

pillars, aphids and spider mites as indicated below.

Biological activity 5 Applied against Active agent, Percent percent deaths coneenof pests tration 0.2 100 Caterpillars (Plutclla maculipennis) 0.02 100 0.002 50 0.2 100 Aphids (DoraZis fabae) 0.02 100 0.002 100 Spider mites (Tctranychus telarius green resistant) 0.2 100 i 0.02 80 We claim: 1. A compound of the formula (Pu)n O(HJOHQ (CH =OHCH N 0 wherein R is a member selected from the group consisting of methyl and chloro and n is an integer of 1-2, It being defined as 1 when R is chloro and as 2 when R is methyl; the diallyl amino moiety being attached to the phenyl ring in ortho position when R is chloro and in para-position when R' is defined as a methyl group. 2. A compound of the following formula (CIIz=CHOH2)zN- Ofi-NHCH 3. A compound of the formula o NrrcH;

0 a I I(CH 0H=CH 4. A compound of the formula Cl- Ofi/NHCH3 N(CH -CH=CH2)2 5. A compound of the formula @oA -Nntlih N(CH -CI-I=CH2)z References Cited by the Examiner UNITED STATES PATENTS 2,843,519 7/58 Fitch 167-30 2,854,374 9/58 Huisman et a1. 16730 2,984,682 5/61 Kaeding 260479 30 3,060,225 10/62 Shulgin 260479 FOREIGN PATENTS 446,303 1/48 Canada.

OTHER REFERENCES LORRAINE A. WEINBERGER, Primary Examiner. A. LOUIS MONOCELL, LEON ZITVER, Examiners.

Kolbezen et al.: Journal Agric. and Food Chem., 2, 

1. A COMPOUND OF THE FORMULA 